Quaternary ammonium compounds



United States Patent 3,290,374 QUATERNARY AMMONIUM COMPOUNDS Eugene Kraiman, Cedar Grove, NJ., and Arthur F. Hasson, Woodside, N.Y., assignors to Sun Chemical Corporation, New York, N.Y., a corporation of Delaware No Drawing. Filed Apr. 24, 1963, Ser. No. 275,224 12 Claims. (Cl. 260-561) This invention relates to new organic ammonium compositions which display germicidal, fungicidal, bactericidal and herbicidal properties. More specifically this invention relates to quaternary ammonium salts formed by the reaction of tertiary amines with halo-alkyl amidochlorals to provide commercially attractive quaternary compounds having higher anti-microbial activity than the commercial preparations heretofore available.

The quaternary ammonium compositions are illustrated by the following general formula wherein A represents an alkylene group having from 1 to 6 carbon atoms, R represents a halogen, R and R", which may be the same or different and may be the same as R or a hydrogen, R represents an acylic hydrocarbon group having from 10 to 18 carbon atoms, R and R which may be the same or different, represent an alkyl, alkoxy and hydroxy alkyl groups (or alkyl ethers thereof), having from 1 to 4 carbon atoms per alkyl group and X represents a water soluble anion.-

Compounds having the above formula may be prepared by several different methods. For instance, these compounds may be prepared by the condensation reaction of a halogenated alkyl amide with a halogenated aldehyde. The product obtained from the reaction of a halogenated alkyl amide with a halogenated aldehyde may be illustrated by-the following formula:

R H o R(3-( 1=N i in which A, R, R, R" represent the molecular groups referred to above and X represents a halogen. The halogenated alkyl arnido-chloral is then reacted with a tertiary amine having the following formula:

/Ra Rr-N I wherein R represents an acylic alkyl group having from 10 to 18 carbon atoms; R and R which may be the same or different is an alkyl, alkoxy, hydroxy alkyl group (or alkyl ethers thereof) having from 1 to 4 carbon atoms per alkyl group in the presence of a suitable solvent at a temperature from 50C. to about 150 C. to yield a quaternary ammonium salt.

The amides employed in this reaction are halogenated alkyl amides wherein the alkyl group has from 1 to 6 carbon atoms. Examples of halogenated alkyl amides are chloro-acetamide, chloro-propionamide, butanamide, chloro-2-methylpropanamide, chloro-pentanamide, and chloro-hexanamide. Halogen radicals such as bromine and iodine may be substituted for chlorine in th above compounds.

chloro- Amines such as aliphatic tertiary amines may be employed in this reaction. The alkyl group represented by R above may be an acylic alkyl group having from 10 to 18 carbon atoms, preferably having from 12 to 16 carbon atoms and more preferably having from 12 to 15 carbon atoms. Examples of such alkyl groups are decyl, undecyl, dodecyl, pentadecyl, hexadecyl, octadecyl, etc. The other groups connected to the nitrogen atom of the tertiary amine are represented by R and R above and may be alkyl, alkoxy and hydroxy alkyl groups (or alkyl ethers thereof), wherein the alkyl group is a lower alkyl group having from 1 to 4 carbon atoms, preferably from 1 to 2 carbon atoms, such as methyl, ethyl, propyl and butyl; an alkoxy group wherein the alkyl portion has from 1 to 4 carbon atoms, preferably from 1 to 2 carbon atoms such as methyl, ethyl,

propyl and butyl and hydroxy alkyl groups and alkyl ethers derived therefrom, wherein the alkyl group contains 4 carbon atoms or less such as, for example, methyl ether, ethyl ether, propyl ether and butyl ether and mixtures thereof. Examples of tertiary amines which may be employed are decyldimethylamine, undecyldimethylamine, decylmethylethylamine, decyldiethylamine, dodecyldimethylamine, pentadecyldibutylamine, pentadecyldimethylamine, hexadecyldipropylamine, tridecyldimethylamine, tetradecyldimethylamine and octadecyldimethylamine and so on.

Since the cationic portion of the above quaternary ammonium germicides is the reactive component, the salt forming radicals are not generally regarded as being critical in nature; therefore, any anionic radicals which are capable of yielding water soluble salts can be used such -as for example halides, a free base such as hydroxide or other anions of a water soluble acid which yields water soluble salts such as nitrates, sulfates, alkyl sulfates, phosphates, ortho phosphates, metaphosphates, pyrophosphates, formates, acetates, lactates, tartrates, citrates, etc. Halides such as chlorides and bromides are preferred and short chain alkyl sulfates, such as meth-osulfate and ethosulfate are the more desirable alkyl sulfates contemplated as anionic radicals. r

.In carrying out this invention, the halogenated alkyl amide-halogenated aldehyde compound is mixed with a tertiary amine and reacted in quantities such that the halogenated alkyl-amide-halogenated aldehyde to tertiary amine ratio is from about 0.9:1 to 1.221, preferably the ratio should be 1:1 or very nearly 1:1 in order to obtain substantially complete reaction of the reactants. As mentioned above, the reaction between the halogenated alkyl amide-halogenated aldehyde and the tertiary amine is preferably carried out in the presence of a solvent. Where a solution of the quaternary ammonium composition is desired it is preferable that the solvent dissolve both the reactant and the product; however, where a solid quaternary ammonium compound is desired, a solvent should be selected which will dissolve the reactant but not the product. In some cases the reaction may be initiated in the absence of a solvent followed by the addition of a solvent in the latter stages of the reaction. Suitable solvents which may be employed in the reaction are, for example, water, aliphatic alcohols, having not more than 8 carbon atoms, such as methanol, ethanol, propa-nol, isopropanol, butanol, hexanol, octanol, ethylene glycol, propylene glycol, glycerol, etc. Other solvents which may be employed are ketones such as 3-pentanone, 2-methyl-3-butanone, Z-butanone, 2-hexan-one,

dimethyl ketone, 3-hexanone cyclopentanone, 2-4 pentanedione, etc. Esters, such as ethyl acetate, propyl acetate, methyl propionate, isopropylacetate, ethyl isobutyrate, butyl acetate, amyl acetate, n-hexyl acetate, etc., aliphatic and aromatic hydrocarbons, such as, for example, pentane, hexane, heptane, octane, nonane, decane, cyclohexane, benzene etc., may also be employed as solvents in this reaction.

The actual temperature employed in the condensation reaction is not critical and may vary from about 50 C. to about 150 C., with the preferred ranges being from about 60 C. to 100 C. In view of the fact that the particular reactants used may be selected from a large list and since the best operating temperature depends largely upon the specific reactants employed, it is thus apparent that the temperature may be varied without effecting the yield of desired product. It is to be understood, however, that higher or lower temperatures may be employed than those specified above, with a resultant increase or decrease in reaction rate in accordance with the general law of chemical reactions. The use of pressure above as well as below atmospheric may be employed. However, it has been found that the reaction may be carried out at atmospheric pressure without materially effecting the yield of reaction product. In some cases, where a low boiling reactant or solvent is employed in the reaction, it may be desirable to employ a pressure higher than atmospheric. Generally the reaction time will vary with the temperature, the higher the temperature, the shorter the reaction time. It is preferred that the reaction be carried out from 1 to 10 hours and, more preferably, from 2 to hours. The quaternary ammonium salts thus prepared in accordance with this invention can be used in either the crude state or they may be separated from the reaction mixture by any conventional means known to the art, such as, evaporation, filtration, distillation, centrifugation and the like.

In order to further describe the invention without intent of limitations, the following illustrative embodiments are set forth.

Example I 25.3 grams of the compound obtained from the reaction of chloral and chloro-acetamide were reacted with 22.5 grams of n-tetradecyldimethylamine in the presence of 47.9 grams of ethyl acetate. The mixture was refluxed at a temperature of from 85 C. to 95 C. for a period of 5 hours. At the end of the reaction period the reaction mixture was cooled to room temperature and a colorless crystalline solid precipitated therefrom. The crystalline material was separated from the reaction mixture by filtration and analyzed. Analysis of the product dis closed that approximately 39 grams of a quaternary ammonium salt having the formula l l H R3 wherein R is an acyclic hydrocarbon having 14 carbon atoms, R and R are methyl groups and X is a chloride, was recovered from the reaction. This compound, when tested by the A.O.A.C. Use'Dilution Test against Salmonella choleraesuis, showed kills out of 10 at a concentration of 300 p.p.m. active. This test specifies dilution of the active compound with distilled water. In addition, this quaternary ammonium salt has a Hard Water Tolerance of 450 p.p.m. (Chambers test).

Example II 33.75 grams of a compound obtained from the condensation reactionof chloroacetamide and chloral were reacted with 31.5 grams of a mixed n-alkyldimethylamine to 40% n-tridecyldimethylamine, 35 to 40% n-tetradecyldimethylamine and 15 to 20% n-pentadecyldimethylamine) in the presence of 68.8 grams of 99% isopropanol. The mixture was refluxed at a temperature of about C. to C. with agitation for a period of about 5 hours. Analysis of the reaction solution by silver nitrate titration indicated a conversion of about 89 percent. This solution containing a mixture of quaternary ammonium salts, when tested according to the A.O.A.C. Use Dilu tion Test, gave 8 kills out of 10 against Staphylococcus aureus and 9 kills out of 10 against Salmonella choleraesuis at a concentration of 200 ppm. active.

Surprisingly, it was found that the quaternary ammonium salts and, in particular, a quaternary ammonium chloride, having an alkyl group of 14 carbon atoms attached to the pentavalent nitrogen atom was the most effective germicidal compound. However, it has also been shown that a mixture of quaternary ammonium compounds having from 12 to 15 carbon atoms connected to the pentavalent nitrogen atom are equally effective as germicidal compositions.

The compounds made in accordance with this invention are practically odorless and relatively non-toxic to man and have proven suitable for various preserving and disinfecting purposes. These new compounds may be used in dilution with hard water without diminution of their activity. Aqueous solutions of these new compounds can be used for disinfecting rooms, floors, medical instruments and the like.

While there is disclosed above but a limited number of the embodiments of the invention herein presented, it is possible to provide still other embodiments without departing from the inventive concepts herein disclosed and it is desired, therefore, that only such limitations be imposed on the appended claims as herein stated.

What is claimed is:

1. A quaternary ammonium compound of the formula:

wherein A is an alkylene group having from 1 to 6 carbon atoms, R is a halide, R and R are selected from' the group consisting of a halide or hydrogen; R is an alkyl group having from 10 to 18 carbon atoms; R and R are selected from the group consisting of alkyl, alkoxy, hydroxy alkyl and alkyl ethers thereof having from 1 to 4 carbon atoms per alkyl group and X is a water soluble anion.

2. A quaternary ammonium compound as defined in claim 1 wherein R is a halide.

3. A quaternary ammonium compound as defined in claim 1 wherein R and R are halides.

4. A quaternary ammonium compound as defined in claim 1 wherein R and R" are chlorides.

5. A quaternary ammonium compound as defined in claim 1 wherein the water soluble anion is a halide.

6. A quaternary ammonium compound as defined in claim 1 wherein the water soluble anion is a chloride.

7. A quaternary ammonium compound as defined in claim 2 wherein the water soluble anion is a halide.

8. A quaternary ammonium compound as defined in claim 3 wherein the water soluble anion is a halide.

9. A quaternary ammonium compound as defined in claim 3 wherein R and R are methyl groups.

10. A quaternary ammonium compound as defined in claim l wherein A is a methylene group.

11. A quaternary ammonium compound as defined in claim 9 wherein A is a methylene group.

5 12. A quaternary ammonium compound of the formula:

1 a t R1 o1- :-o= -(|1-C- R2 x- 01 H Ra wherein R is an acyclic hydrocarbon having 14 carbon atoms; R and R are methyl groups and X is a chloride.

ReferencesvCited by the Examiner UNITED STATES PATENTS 2,410,862 11/1946 Bousquet et a1. 16722 Stone 167-22 Pe-rolano et a1. 260561 X Frankel et a1 260561 Klagcr 260561 Shapiro et a1 260-561 X WALTER A. MODANCE, Primary Examine r.

JULIAN S. LEVITT, Examiner.

10 GEORGE A. MENTIS, NATALIE TROUSOF,

Assistant Examiners. 

1. A QUATERNARY AMMONIUM COMPOUND OF THE FORMULA: 